Method for butenyl cyclohexenes



United States Patent -METHOD FOR BUTEN YL CYCLOHEXENES Wolfgang Schneider, Broadview Heights, Ohio, assignor to The B. F. Goodrich Company, New York, N.Y., a

3,408,416 Patented Oct. 29, 1968 as benzene or-toluene. Either catalyst component may be charged first and the other added gradually thereto while stirring the entire reaction mixture. This reaction mixture, prepared in situ or separately, is heated in the presence corporation of New York of the olefins preferably at a temperature of about -20 No Drawing. Filed on. 20, 1966, Ser. No. 587,954 Preferably The Claims (CL 260 666) s conducted under sufficient pressure to keep the reactants in liquid state. This Wlll depend-on the temperature of reaction. After the reaction the excess alpha-olefin is redh 't'll 1t thd' ABS CT OF THE DISCLOSURE 10 gi cviefiztgn t e product disi ed to 1so ae e esired Butenyl cyclohexene is prepared from ethylene and EXAMPLE vinyl cyclohexene g q g i m g 3 2 In a series of preparations, the nickel complex in vinylgi q q i i e slllc cyclohexene was charged to an oxygenand moisturei i i lsdumaril on e free reactor. The aluminum or boron halide in vinylcyclouniary g me e an an a ummum a 1 e or own hexene was slowly added with stirring. The resulting mixhahde et erate' ture was then charged to an autoclave which was purged with argon and then sealed and pressured with ethylene. This invention relates to an improved method for pre- The autoclave was heated to 80". After 1.5 to 65 hours paring butenyl cyclohexenes. the pressure was released and the reaction products dis- Butenyl cyclohexen is prepared by dimerizing ethylene tilled off. The reactants and amounts, and product diswith vinyl cyclohexene in accordance with this invention tribution, are set forth in the table.

TABLE Nickel complexes:

Bisacrylonitrile nickel (grams) .7

Bisacrolein nickel (grams) B siumarylnitrile nickel (grams) Bisfumaryl chloride nickel (grams)- Metal halides:

Diisobutyl aluminum chloride (ml.) 2 Ethyl aluminum sesquichloride (ml.) 10 Diethyl aluminum chloride (m1) Aluminum bromide (grams) Boron halide etherate (1111.)

Starting materials:

4-vinyl cyclohexene (grams) 1,512 90 83 90 90 80 90 Ethylene (grams) 470 51 44 40 52 42 Time (hours) 1. 5 40 40 45 45 45 Product Analysis (percen Vinyl cyclohexene 7. 3 27 6. 2 71 1 18 69 Ethylidene cyclohexene 20. 8 41 8. 6 5 40 9 1 4(1-butenyl) cyclohexene 62. 5 32 64. 2 24 48 54 22 4(alpha-methylene propyl) cyclohexene- 9. 4 21 11 19 8 in improved yields by reacting ethylene with vinyl cyclohexene in the presence of a nickel complex mixed with an aluminum halide or a boron etherate.

The nickel complexes include, for example, bisacrolein nickel, bisacrylonitrile nickel, bisfumaronitrile nickel, bisfumarylchloride nickel, biscinnamonitrile nickel, biscinnamylchloride nickel, and biscinnamaldehyde nickel. The complex nickel compounds are easily prepared by refluxing nickel carbonyl with acrylonitrile, acrolein and the like. Other useful coordination compounds include pure nickel olefin complexes such as bis(cyclooctadiene 1,5) nickel and the like.

The aluminum halides include aluminum chloride, aluminum bromide and alkyl aluminum halides of the formula R AlX wherein X is chlorine or bromine and R is an alkyl radical containing 2 to 12 carbon atoms. Typical alkyl aluminum halides include dialkyl aluminum halides and alkyl aluminum dihalides as ethyl aluminum dichloride, dipropyl aluminum chloride, diisobutyl aluminum chloride, butyl aluminum dichloride, dihexyl aluminum bromide, ethyl aluminum sesquichloride and the like, where R+X=3.

The amount of the two catalyst components used may be varied from about 0.0001 to 10 millimols, preferably about 0.001 to l, per mol of olefins, in a molar ratio of greater than one mol of alkyl halide per mol of nickel complex up to a molar ratio of 10 to 1 and the same ratio for the boron halide.

The catalyst may be prepared by adding the components separately to a reactor, preferably either in the ethylene or vinylcyclohexene or in an inert solvent such The boron halide may be the iodide, chloride, bromide or fluoride.

The 4(1 butenyl)cyclohexene is readily isomerized by known methods to 4(3 butenyl)cyclohexene which then can be interpolymerized with ethylene or ethylene and propylene with a reduced titanium or Ziegler type catalyst to provide a sulfur-curable elastomer.

I claim: 7

1. The method of preparing butenyl cyclohexene which comprises contacting ethylene and vinyl cyclohexene with a halide selected from the group consisting of aluminum halides and boron halide etherates; and a nickel complex selected from the group consisting of bisacrolein nickel, bisacrylonitrile nickel, bisfumaronitrile nickel, bisfumarylchloride nickel, biscinnamonitrile nickel, biscinnamylchloride nickel, and biscinnamaldehyde nickel.

2. The method of claim 1 wherein the nickel complex and aluminum halide are present in a molar ratio of greater than one mol of aluminum halide per mol of nickel complex.

3. The method of claim 2 wherein the aluminum halide is aluminum chloride or aluminum bromide.

4. The method of claim 1 wherein the boron halide etherate is BF3(C2H5)2O.

5. The method of claim 2 wherein the aluminum halide is an alkyl aluminum halide of the formula wherein X is selected from the group consisting of chlorine and bromine and R is an alkyl radical containing 2 to 12 carbon atoms and R+X=3.

6. The method of claim 5 wherein X is chlorine and References Cited R contains 2 to 4 carbon atoms. l I

7. The method of claim 6 wherein the nickel complex UN TED STATES PATENTS is bisacrylonitrile nickeL 2,969,408 1/1961 NOW11 n et a1 260683.l5 8. The method of claim 6 wherein the nickel complex 5 337L879 9/1966 stably 260666 is bisacrolein nickeL 3,152,158 10/1964 Clark 260-666 9. The method of claim 6 wherein the nickel complex is bisfumarylnitrile nickel. E t 10. The method of claim 6 wherein the nickel complex F S m xamw is bisfumaryl chloride nickel. 10

K EF i r f v 

